CA1244422A - Quinophthalone compounds, processes for producing them, and their use as dyes - Google Patents
Quinophthalone compounds, processes for producing them, and their use as dyesInfo
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- CA1244422A CA1244422A CA000423081A CA423081A CA1244422A CA 1244422 A CA1244422 A CA 1244422A CA 000423081 A CA000423081 A CA 000423081A CA 423081 A CA423081 A CA 423081A CA 1244422 A CA1244422 A CA 1244422A
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/28—Colorants ; Pigments or opacifying agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B25/00—Quinophthalones
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
- Paper (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Plural Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Cosmetics (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Quinophthalone compounds processes for producing them, and their use for dyeing and printing textile materials, paper and leather, and for the preparation of inks.
Abstract There are described novel cationic quinophthalone compounds of the formula I
I
wherein the symbols have the meanings defined in Claim 1, and also processes for producing them. These novel quinophthalone compounds can be used in particular as dyes for dyeing and printing paper, greenish yellow dyeings having good fastness to water and to light being obtained.
Abstract There are described novel cationic quinophthalone compounds of the formula I
I
wherein the symbols have the meanings defined in Claim 1, and also processes for producing them. These novel quinophthalone compounds can be used in particular as dyes for dyeing and printing paper, greenish yellow dyeings having good fastness to water and to light being obtained.
Description
~'Z~f~4 Case 1-13837/=
Quinophthalone compounds, processes for producing them, and their use for dyeing and printing textile materials, paper and leatherL_and for the preparation of inks The invention relates to novel quinophthalone compounds of the formula I
~ N~ i1 A~ Z-~(Q)n(~)AD(3 wherein Y is either a substituent of the formula ~ - or or a benzene ring which is annularly-linked in the S/6- or 7/8-position, and these substituents and benzene rings can be substituted;
Z is a polyvalent bridge member;
Q is a cationic radical of the formula 1~2 5 R
lZ9~49LZZ
in which Rl to ~6 independently of one another are each an unsubstituted or substituted cl-C4-alkyl group, or Rl and Rz or R3 and R4 or R3 and R4 and R5 . together with the N atom form in each case a hetero-cyclic ring;
m is 1 or 2, preferably 1;
n is 1 or 2, especially 1; and An is an anion;
and wherein the nuclei A and /or B can be substituted.
The defined substituent Y or annularly-linked benzene ring Y can be substituted. Substituents are for example:
the OH group, a Cl-C4-alkyl group (straight-chain or branched-chain) or halogen, such as fluorine, chlorine or bromine.
In preferred quinophthalone compounds, Y is in particular the substituent of the formula N~ N~ 0~
~c~ \s/ ~ ~ or ~-~ ~N~ `
or a benzene ring annularly-linked in the 5/6- or 7/8-position.
In the case of the polyvalent bridge-member Z, it is for example any one of the followi.ng groups:
-N-H -N-CO-alkylene(Cl-C4)-, -CH2-, alkylene(Cl~C4)~, (H, alkyl Cl-C4) -CONH-alkylene(Ci-C4)-, -S02NH-alkylene(Cl-C4)-, ~244~ZZ
-CH2-NHCO-alkylene(Cl-C4)- or / (H,alkyl Cl-C4) ; !\ (alkylene Cl-C4)~
_N~ (H~alkyl Cl-C4) (alkylene Cl-C4)-I(H,alkyl. Cl-C4) wherein each of the alkyl and alkylene groups can be further - substituted, for example by OH, halogen (F, Cl or ~r), NH2 and ~N-alkyl Cl-C4.
Preferred bridge members Z are:
-NH-CH2CH(OH)-CH2- , -CH2-NHCO-alkylene(Cl-C4)- especially -CH2-NHCO-CH2- and -CH2-NHCO-CH~-~H2, -N-CO-alkylene(Cl-C4)-, particularly , (H,alkyl Cl-C4) (CH2)3 NH (CH2) 3--NHCO-CH2- and ~ !~
-NH- ~ ~. -NH ( CH2) 3 When Rl to R6 are each a substituted Cl-C4-alkyl group, a possible substituent is especially the -OH, -NH2, -N(alkyl 1-4)2 or phenyl group.
Where Rl and R2 and/or R3 and.R4 including the N atom in each case form a heterocyclic ring, this is for example:
the morpholine, pyrrolidine, piperidine, piperazine, imidazole or triazole ringO
If R3 and R4 together with R5 form, with the inclusion of the N atom, a heterocyclic ring, this is for example an unsubstituted or substituted (for example by Cl-C4-alkyl) pyridinium ring, or a triethylenediamine ring of ~Z~4Z2 the formula or -N ~ ~--`N- alkyl Cl-C4 wherein the alkyl group bound to the cationic N atom can also be substituted, for example by NH2, NH-alkyl-Cl-C4 and N(alkyl Cl-C4)2.
Q as the cationic radical according to definition is for example any one of the following radicals:
~3/CH3 ~ C2H5 ~/C2H4H
NH2 ~ N NH2 ~ N' ~H2 ,, C2H5 C2H40H
; - N~ H¦ ~ -N~ H ~- , -N~ H ~0 , -N~ H ~ , ~H2 -N(CH3)3 , -N(C2H~OH)3 , -N~ ~- , -Nl~ H ~-
Quinophthalone compounds, processes for producing them, and their use for dyeing and printing textile materials, paper and leatherL_and for the preparation of inks The invention relates to novel quinophthalone compounds of the formula I
~ N~ i1 A~ Z-~(Q)n(~)AD(3 wherein Y is either a substituent of the formula ~ - or or a benzene ring which is annularly-linked in the S/6- or 7/8-position, and these substituents and benzene rings can be substituted;
Z is a polyvalent bridge member;
Q is a cationic radical of the formula 1~2 5 R
lZ9~49LZZ
in which Rl to ~6 independently of one another are each an unsubstituted or substituted cl-C4-alkyl group, or Rl and Rz or R3 and R4 or R3 and R4 and R5 . together with the N atom form in each case a hetero-cyclic ring;
m is 1 or 2, preferably 1;
n is 1 or 2, especially 1; and An is an anion;
and wherein the nuclei A and /or B can be substituted.
The defined substituent Y or annularly-linked benzene ring Y can be substituted. Substituents are for example:
the OH group, a Cl-C4-alkyl group (straight-chain or branched-chain) or halogen, such as fluorine, chlorine or bromine.
In preferred quinophthalone compounds, Y is in particular the substituent of the formula N~ N~ 0~
~c~ \s/ ~ ~ or ~-~ ~N~ `
or a benzene ring annularly-linked in the 5/6- or 7/8-position.
In the case of the polyvalent bridge-member Z, it is for example any one of the followi.ng groups:
-N-H -N-CO-alkylene(Cl-C4)-, -CH2-, alkylene(Cl~C4)~, (H, alkyl Cl-C4) -CONH-alkylene(Ci-C4)-, -S02NH-alkylene(Cl-C4)-, ~244~ZZ
-CH2-NHCO-alkylene(Cl-C4)- or / (H,alkyl Cl-C4) ; !\ (alkylene Cl-C4)~
_N~ (H~alkyl Cl-C4) (alkylene Cl-C4)-I(H,alkyl. Cl-C4) wherein each of the alkyl and alkylene groups can be further - substituted, for example by OH, halogen (F, Cl or ~r), NH2 and ~N-alkyl Cl-C4.
Preferred bridge members Z are:
-NH-CH2CH(OH)-CH2- , -CH2-NHCO-alkylene(Cl-C4)- especially -CH2-NHCO-CH2- and -CH2-NHCO-CH~-~H2, -N-CO-alkylene(Cl-C4)-, particularly , (H,alkyl Cl-C4) (CH2)3 NH (CH2) 3--NHCO-CH2- and ~ !~
-NH- ~ ~. -NH ( CH2) 3 When Rl to R6 are each a substituted Cl-C4-alkyl group, a possible substituent is especially the -OH, -NH2, -N(alkyl 1-4)2 or phenyl group.
Where Rl and R2 and/or R3 and.R4 including the N atom in each case form a heterocyclic ring, this is for example:
the morpholine, pyrrolidine, piperidine, piperazine, imidazole or triazole ringO
If R3 and R4 together with R5 form, with the inclusion of the N atom, a heterocyclic ring, this is for example an unsubstituted or substituted (for example by Cl-C4-alkyl) pyridinium ring, or a triethylenediamine ring of ~Z~4Z2 the formula or -N ~ ~--`N- alkyl Cl-C4 wherein the alkyl group bound to the cationic N atom can also be substituted, for example by NH2, NH-alkyl-Cl-C4 and N(alkyl Cl-C4)2.
Q as the cationic radical according to definition is for example any one of the following radicals:
~3/CH3 ~ C2H5 ~/C2H4H
NH2 ~ N NH2 ~ N' ~H2 ,, C2H5 C2H40H
; - N~ H¦ ~ -N~ H ~- , -N~ H ~0 , -N~ H ~ , ~H2 -N(CH3)3 , -N(C2H~OH)3 , -N~ ~- , -Nl~ H ~-
2 5 ( 2 5)3 ' Nl(C2H4H)2 ' -N~ H ~ N/ H O
CH CH3 . C2H5 -N(C2H5)2 , -N H20H , -N~H ¦ ~ -N~H ¦
-N-(CH3)2 ~ ~ H ~ ~ CH _-I I - CH3 2 \.=./
44~Z~
.
(~)/C2H5 ~3~ 3 (~ CH3 -N~OCH3 , -~oC2H5 , -N~ H! ~ N~CH3 2 5 C2H5 OCH~ CH2cH2oH
-~< H ~- , -N~ H ~O , -~ H ~N
In preferred quinophthalone compounds of the formula I, Q is a cationic radical of the formula I ~ -R4 wherein R3, R4 and R5 independently of one another are each an unsubstituted or substituted Cl-C4-alkyl group, in particular a trialkylammonium group, such as a trimethyl-ammonium group, or R3, R4 and R5 together with the N atom form a heterocyclic ring, especially a pyridinium ring of the formula \.=,/
When the nucleus A is substituted, substituents are for example: halogen~ such as fluorine, chlorine or bromine; Cl-C4-alkyl (straight-chain or branched-chain), N02, NH2, NHCO-alkyl(Cl-C4), COO-alkyl(Cl-C4)~ Cl-C4-alkoxy, S-alkyl(Cl-C4), S02-alkyl(Cl-C4), NHC0-phenyl, C00-phenyl, phenoxy, thiophenoxy and S02-phenyl. In the preferred quinophthalone compounds, the nucleus A is not further substituted, or is mono- or polysubstituted by halogen, especially chlorine.
Substituents in the nucleus B are for example the following: halogen, such as fluorine, chlorine or bromine;
-` 124~4;~Z
Cl-C4-alkyl (straight-chain or branched-chain), OH, cl-C4-alkoxy, phenoxy, NH-alkyl(Cl-C4), NH-phenyl, S-alkyl-(Cl-C4), thiophenoxy, S02-alkyl(Cl-C4), S02-phenyl, COO-alkyl(Cl-C4) and COO-phenyl. In the preferred quino-phthalone compounds, the nucleus B is not further substituted.
The grouping -~Z~-m(Q)n~ An ~n can be bound to each benzene or phenyl nucleus, or also to the nucleus B.
The term "Cl-C4-alkyl" denotes here and in the following for example: the methyl, ethyl, n-propyl, iso-propyl, n-butyl or tert-butyl group; this applies analogously also to "Cl-C4-alkylene".
Suitable anions "An" are both inorganic and organic anions; the following are for example mentioned: the halide ion, such as the chloride, bromide or iodide ion, also the sulfate, methylsulfate, borotetrafluoride, aminosulfate, perchlorate, carbonate, bicarbonate, phosphate, phosphomolybdic, phosphotungstic, phospho-tungstomolybdic, benzenesulfonate, naphthalenesulfonate, 4-chlorobenzenesulfonate, oxalate, maleate, acetate, propionate, lactate, succinate, chloroacetate, tartrate, methanesulfonate or benzoate ions, or complex anions, such as those of zinc chloride double salts.
The novel quinophthalone compounds of the formula I
are readily water-soluble products which are obtained in a known manner. One possible production process comprises condensing a quinaldine compound of the formula III
~ Y--+~ B~i (III) with a phthalic anhydride of the formula IV
~LZ4~Z'~
,1 o o\ I! A~! (IV) i to obtain a condensation product of the formula II
~ A i (II) wherein the symbols Y, B and A have the meanings defined under the formula I.
The quinaldine compounds of the formula III are known and can be produced by known methodsO There are used for example the following compounds:
5,6-benzoquinaldine, 7,8-benzoquinaldine, 6-(6'-methyl-benzothiazole)-quinaldine, and 6-benzotriazole-quinaldine.
Likewise known are the phthalic anhydride compounds of the formula IV, which can also be produced by known methods. The following compounds can for example be used:
phthalic anhydride,
CH CH3 . C2H5 -N(C2H5)2 , -N H20H , -N~H ¦ ~ -N~H ¦
-N-(CH3)2 ~ ~ H ~ ~ CH _-I I - CH3 2 \.=./
44~Z~
.
(~)/C2H5 ~3~ 3 (~ CH3 -N~OCH3 , -~oC2H5 , -N~ H! ~ N~CH3 2 5 C2H5 OCH~ CH2cH2oH
-~< H ~- , -N~ H ~O , -~ H ~N
In preferred quinophthalone compounds of the formula I, Q is a cationic radical of the formula I ~ -R4 wherein R3, R4 and R5 independently of one another are each an unsubstituted or substituted Cl-C4-alkyl group, in particular a trialkylammonium group, such as a trimethyl-ammonium group, or R3, R4 and R5 together with the N atom form a heterocyclic ring, especially a pyridinium ring of the formula \.=,/
When the nucleus A is substituted, substituents are for example: halogen~ such as fluorine, chlorine or bromine; Cl-C4-alkyl (straight-chain or branched-chain), N02, NH2, NHCO-alkyl(Cl-C4), COO-alkyl(Cl-C4)~ Cl-C4-alkoxy, S-alkyl(Cl-C4), S02-alkyl(Cl-C4), NHC0-phenyl, C00-phenyl, phenoxy, thiophenoxy and S02-phenyl. In the preferred quinophthalone compounds, the nucleus A is not further substituted, or is mono- or polysubstituted by halogen, especially chlorine.
Substituents in the nucleus B are for example the following: halogen, such as fluorine, chlorine or bromine;
-` 124~4;~Z
Cl-C4-alkyl (straight-chain or branched-chain), OH, cl-C4-alkoxy, phenoxy, NH-alkyl(Cl-C4), NH-phenyl, S-alkyl-(Cl-C4), thiophenoxy, S02-alkyl(Cl-C4), S02-phenyl, COO-alkyl(Cl-C4) and COO-phenyl. In the preferred quino-phthalone compounds, the nucleus B is not further substituted.
The grouping -~Z~-m(Q)n~ An ~n can be bound to each benzene or phenyl nucleus, or also to the nucleus B.
The term "Cl-C4-alkyl" denotes here and in the following for example: the methyl, ethyl, n-propyl, iso-propyl, n-butyl or tert-butyl group; this applies analogously also to "Cl-C4-alkylene".
Suitable anions "An" are both inorganic and organic anions; the following are for example mentioned: the halide ion, such as the chloride, bromide or iodide ion, also the sulfate, methylsulfate, borotetrafluoride, aminosulfate, perchlorate, carbonate, bicarbonate, phosphate, phosphomolybdic, phosphotungstic, phospho-tungstomolybdic, benzenesulfonate, naphthalenesulfonate, 4-chlorobenzenesulfonate, oxalate, maleate, acetate, propionate, lactate, succinate, chloroacetate, tartrate, methanesulfonate or benzoate ions, or complex anions, such as those of zinc chloride double salts.
The novel quinophthalone compounds of the formula I
are readily water-soluble products which are obtained in a known manner. One possible production process comprises condensing a quinaldine compound of the formula III
~ Y--+~ B~i (III) with a phthalic anhydride of the formula IV
~LZ4~Z'~
,1 o o\ I! A~! (IV) i to obtain a condensation product of the formula II
~ A i (II) wherein the symbols Y, B and A have the meanings defined under the formula I.
The quinaldine compounds of the formula III are known and can be produced by known methodsO There are used for example the following compounds:
5,6-benzoquinaldine, 7,8-benzoquinaldine, 6-(6'-methyl-benzothiazole)-quinaldine, and 6-benzotriazole-quinaldine.
Likewise known are the phthalic anhydride compounds of the formula IV, which can also be produced by known methods. The following compounds can for example be used:
phthalic anhydride,
3,4,5,6-tetrachlorophthalic anhydride, 3-nitrophthalic anhydride, and
4-nitrophthalic anhydride.
The condensation reaction of the compound III with IV
proceeds in a known manner (for example: Ann. Chem. Vol.
516, p. 155 [1935~).
Z49L~22 Into this condensation product of the formula II is then introduced the grouping ~~Z)m--~Q)n ~ Ann ~ in stages, depending on the meaning of the symbol Z, as folLows.
a) When Z is a -CH2-NHC0-alkylene t Cl-C4) group, the condensation product of the formula II is reacted with a methylolamide of the formula H0-CH2-NHC0-alkylene-(Cl-C4)-Hal to give a product of the formula IIa ,, ~o\ / ~ OIH ¦--(CH2-NHCO-alkylene-Cl-C4-Hal) ~. N~ \A~! (IIa) (Einhorn reaction, Angew. Chem. 69, 463 (1957)~ The reaction is performed in the presence of concentrated sulfuric acid (for example monohydrate) or phosphoric acid, optionally together with phosphorus pentoxide, at a temperature of 0 to 50C, preferably at room temperature.
A~ter the introduction of this methylolamide, the cationic group Q is introduced. This is effected for example by reacting the terminal halogen atom "Hal" in the formula IIa with a tertiary amine (corresponding to the radical Q), such as trimethylamine or pyridine; or by reacting this terminal halogen atom "Hal" in the formula IIa with a secondary amine (for example dimethylamine), and subsequently quaternising this in a known manner. The quinophthalone compounds of the formula I are obtained in both cases.
A further applicable production process consists in producing the compound (IIa) in situ by reacting the compound (II) with formaldehyde and an amide of the formula NH2C0-alkylene Cl-C4-Hal in the manner described, and then carrying out the further procedure as stated in the foregoing.
-31 24~L4Z~
b) In the case where Z is an -NH-alkyl(Cl-C4) group, a condensation product of the formula II which contains a halogen atom (for example in the nucleus A or B or in a substituent Y) is taken as the starting material, and is reacted with a halogen-amino-alkyl compound of the formula H2N-alkyl(Cl-C4)-Hal to obtain a product of the formula IIb ~ OH _(~H-alkyl(Cl C4)-Hal)m L o~ ~ (IIb) The introduction of the cationic group Q is subsequently effected as described in the process variant a).
A further production possibility is to use a condensation product of the formula II containing an amino group (for example in the nucleus A or B or in a substituent Y) as the starting material, and to react this with an epoxy compound, for example with the compound of the formula~
; C~2/cH2-cH2 Hal or C~2~CH2-CH2-Q
to give a product of the formula . O OH
Y ~ H-CH -CH-CH -Hal (A) , ~./ \N// ! i! A !
. ~ OH
O
or ~ I 11 A i --t~H-CH2-CH-CH2-Q (B), 4~4~2 the "Hal" atom in product A being subsequently replaced with the radical Q.
c) Where Z is a -CH2 group, the introduction of this group into the condensation product of the formula II
is performed for example by reacting this with formaldehyde and hydrochloric acid to a product of the formula IIc !
. / ~ . I o l(CH2-Hal)m (IIC) .
~ N~ ,A~
The introduction of the cationic group Q is subsequently effected in the manner described under process variant a).
d) If the symbol Z is a -CONH-alkylene(Cl-C4) group or an -S02NH-alkylene(Cl-C4) group, a condensation product of the formula II containing a COOH or S03H group (for example in the nucleus A or B) is advantageously used as the starting material, and this is reacted with a halogen-amino-alkyl compound NH2-alkylene(Cl-C~)-Hal to obtain a product of the formula IId I
. / ~ O,H --(CONH-alkylene(Cl-C4)-Hal)m ~ b~ A~I (IIdl) or a product of the formula IId2 . ./ ~ ~ (so2NH-alkylene(cl-c4) -Hal)m : Y 11 I B I ~
.~ N~ A~ I ( I I d2 ) -20 The introduction of the cationic group Q is subsequently ~` lZ4~9LZZ
effected in the manner described under process variant a).
e) When Z is the grouping (H, alkyl-Cl-C4) ~ (alkylene-Cl~C4)~
-N-~ ~ - N/ (H~ alkyl-Cl-C4) I ~ \ (alkylene-Cl C4)-I (h, alkyl-cl-c4) this grouping is advantageously introduced by starting with a condensation product of the formula II containing an amino group, and reacting ~his product with cyanuric chloride (optionally also cyanuric fluoride) to give a compound of the formula IIe ~, (F) ~1 . . /~ H ~-- N-~ -Cl(F) (IIe).
Y 11 ! B ! .~ N
, \-~ \N~ i!,A~! - (] I, alkyl-Cl-C4) m 10 This compo~md IIe is subsequently reacted with two mols of a diaminoalkyl compound of the formula H2N[alkyl-Cl-C4-N(alkyl-Cl-C4)2] or HN[alkyl-Cl-C4-N(alkyl-cl-c4)2]
and the terminal dialkylamino group is quaternised to obtain the group Q as de-fined.
f) Where Z is the grouping -N-C0-alkylene-Cl-C4- , this ~ H, alkyl-Cl-C4) group can be introduced for example by starting with a condensation product of the formula II containing an amino group, and reacting this product with a compound of the 20 formula Hal-C0-alkylene-Cl-C4-Hal, with subsequent introduction of the cationic group Q in the manner described in the process variant a).
~Z ~4Z;Z
The novel quinophthalone compounds of the formula I
are used in particular as dyes for dyeing and printing textile materials, paper or leather, and for preparing inks.
In cases where these dyes are used for dyeing and printing textile materials, suitable as such are wool, silk and polyamide materials modified with acid groups; as well as polyacrylonitrile materials, especially in the form of wet tow; and also modified polyester materials dyeable with basic dyes. Also suitable are natural and regenerated cellulose materials, specially cotton and viscose, with brilliant yellow dyeings being in part obtainedO The dyes of the formula I according to the invention have on these materials, particularly on the stated cellulose materials, good substantivity, a high degree of exhaustion and a good build-up; and the dyeings ob~ained have good fastness properties, especially good fastness to wet processing and to light.
The novel dyes are suitable also for dyeing polyacrylo-nitrile in the spinning solution.
A preferred use of the dyes of the formula I accordingto the invention is for the dyeing of paper of all types, particularly bleached and sized, lignin-free paper, and also semi-cardboard and cardboard. These dyes are more especially suitable for dyeing unsized paper (for example serviettes) by virtue of the very high standard affinity of the dyes for this substrate.
The dyes according to the invention exhawst very well onto these substrates, the waste liquors - even with deep shades (up to above 1/1 RT - reference type strength) -being left colourless, a factor which is of great technical and ecological advantage, especially in view of the lZ~ Z'~
present-day effluent laws. The high degree of exhaustion is advantageous also with regard to good reproducibility of the shade. Furthermore, the degree of exhaustion is virtually unaffected by the hardness of the water. The dyeings are fast to wetting, that is to say, they exhibit no tendency to bleed when dyed paper in the wet state is brought into contact with moist white paper. This property is particularly desirable for serviettes, in the case of which it is foreseeable that the dyed paper in the wet condition (for example soaked with water, alcohol, tenside solution~ and so forth) will come into contact with other surfaces, such as textiles, paper, and the like~
which have to be protected against soiling.
The good affinity for paper ancd the high degree of exhaustion of the dyes according to the invention, combined with very good build-up properties, are of great advantage for the continuous dyeing of paper, and render possible a very broad and economical application of these novel dyes. They have the following advantages:
a) an easier and more rapid correction of the shade, and therefore less loss of paper not conforming to type (scrap~;
b) a better constancy of shade (no "tailing'l)j and c) there is no necessity to thoroughly clean the stirring vat after each batch, the working process simultaneously being shortened and the process thus optimized.
The yellow dyeings are brilliant and have very good fastness properties, especially fastness to light.
The dyes of the formula I are suitable also for dyeing leather materials by the widest variety of application methods, such as spraying, brushing and dipping, and for "
preparing inks of all types, such as for ball-point pens and for printing inks.
The invention is further illustrated by the following Examples without being limited by them. The temperatures are in degrees centigrade, 'parts' denote parts by weight, and percentages are per cent by weight.
The abbreviation RKN is a quali-ty designation, and indicates the degree of purity of the ceLlulose; the abbreviation SR = Schopper-Riegler denotes the freeness value.
Example 1: 16 parts of the condensation product from
The condensation reaction of the compound III with IV
proceeds in a known manner (for example: Ann. Chem. Vol.
516, p. 155 [1935~).
Z49L~22 Into this condensation product of the formula II is then introduced the grouping ~~Z)m--~Q)n ~ Ann ~ in stages, depending on the meaning of the symbol Z, as folLows.
a) When Z is a -CH2-NHC0-alkylene t Cl-C4) group, the condensation product of the formula II is reacted with a methylolamide of the formula H0-CH2-NHC0-alkylene-(Cl-C4)-Hal to give a product of the formula IIa ,, ~o\ / ~ OIH ¦--(CH2-NHCO-alkylene-Cl-C4-Hal) ~. N~ \A~! (IIa) (Einhorn reaction, Angew. Chem. 69, 463 (1957)~ The reaction is performed in the presence of concentrated sulfuric acid (for example monohydrate) or phosphoric acid, optionally together with phosphorus pentoxide, at a temperature of 0 to 50C, preferably at room temperature.
A~ter the introduction of this methylolamide, the cationic group Q is introduced. This is effected for example by reacting the terminal halogen atom "Hal" in the formula IIa with a tertiary amine (corresponding to the radical Q), such as trimethylamine or pyridine; or by reacting this terminal halogen atom "Hal" in the formula IIa with a secondary amine (for example dimethylamine), and subsequently quaternising this in a known manner. The quinophthalone compounds of the formula I are obtained in both cases.
A further applicable production process consists in producing the compound (IIa) in situ by reacting the compound (II) with formaldehyde and an amide of the formula NH2C0-alkylene Cl-C4-Hal in the manner described, and then carrying out the further procedure as stated in the foregoing.
-31 24~L4Z~
b) In the case where Z is an -NH-alkyl(Cl-C4) group, a condensation product of the formula II which contains a halogen atom (for example in the nucleus A or B or in a substituent Y) is taken as the starting material, and is reacted with a halogen-amino-alkyl compound of the formula H2N-alkyl(Cl-C4)-Hal to obtain a product of the formula IIb ~ OH _(~H-alkyl(Cl C4)-Hal)m L o~ ~ (IIb) The introduction of the cationic group Q is subsequently effected as described in the process variant a).
A further production possibility is to use a condensation product of the formula II containing an amino group (for example in the nucleus A or B or in a substituent Y) as the starting material, and to react this with an epoxy compound, for example with the compound of the formula~
; C~2/cH2-cH2 Hal or C~2~CH2-CH2-Q
to give a product of the formula . O OH
Y ~ H-CH -CH-CH -Hal (A) , ~./ \N// ! i! A !
. ~ OH
O
or ~ I 11 A i --t~H-CH2-CH-CH2-Q (B), 4~4~2 the "Hal" atom in product A being subsequently replaced with the radical Q.
c) Where Z is a -CH2 group, the introduction of this group into the condensation product of the formula II
is performed for example by reacting this with formaldehyde and hydrochloric acid to a product of the formula IIc !
. / ~ . I o l(CH2-Hal)m (IIC) .
~ N~ ,A~
The introduction of the cationic group Q is subsequently effected in the manner described under process variant a).
d) If the symbol Z is a -CONH-alkylene(Cl-C4) group or an -S02NH-alkylene(Cl-C4) group, a condensation product of the formula II containing a COOH or S03H group (for example in the nucleus A or B) is advantageously used as the starting material, and this is reacted with a halogen-amino-alkyl compound NH2-alkylene(Cl-C~)-Hal to obtain a product of the formula IId I
. / ~ O,H --(CONH-alkylene(Cl-C4)-Hal)m ~ b~ A~I (IIdl) or a product of the formula IId2 . ./ ~ ~ (so2NH-alkylene(cl-c4) -Hal)m : Y 11 I B I ~
.~ N~ A~ I ( I I d2 ) -20 The introduction of the cationic group Q is subsequently ~` lZ4~9LZZ
effected in the manner described under process variant a).
e) When Z is the grouping (H, alkyl-Cl-C4) ~ (alkylene-Cl~C4)~
-N-~ ~ - N/ (H~ alkyl-Cl-C4) I ~ \ (alkylene-Cl C4)-I (h, alkyl-cl-c4) this grouping is advantageously introduced by starting with a condensation product of the formula II containing an amino group, and reacting ~his product with cyanuric chloride (optionally also cyanuric fluoride) to give a compound of the formula IIe ~, (F) ~1 . . /~ H ~-- N-~ -Cl(F) (IIe).
Y 11 ! B ! .~ N
, \-~ \N~ i!,A~! - (] I, alkyl-Cl-C4) m 10 This compo~md IIe is subsequently reacted with two mols of a diaminoalkyl compound of the formula H2N[alkyl-Cl-C4-N(alkyl-Cl-C4)2] or HN[alkyl-Cl-C4-N(alkyl-cl-c4)2]
and the terminal dialkylamino group is quaternised to obtain the group Q as de-fined.
f) Where Z is the grouping -N-C0-alkylene-Cl-C4- , this ~ H, alkyl-Cl-C4) group can be introduced for example by starting with a condensation product of the formula II containing an amino group, and reacting this product with a compound of the 20 formula Hal-C0-alkylene-Cl-C4-Hal, with subsequent introduction of the cationic group Q in the manner described in the process variant a).
~Z ~4Z;Z
The novel quinophthalone compounds of the formula I
are used in particular as dyes for dyeing and printing textile materials, paper or leather, and for preparing inks.
In cases where these dyes are used for dyeing and printing textile materials, suitable as such are wool, silk and polyamide materials modified with acid groups; as well as polyacrylonitrile materials, especially in the form of wet tow; and also modified polyester materials dyeable with basic dyes. Also suitable are natural and regenerated cellulose materials, specially cotton and viscose, with brilliant yellow dyeings being in part obtainedO The dyes of the formula I according to the invention have on these materials, particularly on the stated cellulose materials, good substantivity, a high degree of exhaustion and a good build-up; and the dyeings ob~ained have good fastness properties, especially good fastness to wet processing and to light.
The novel dyes are suitable also for dyeing polyacrylo-nitrile in the spinning solution.
A preferred use of the dyes of the formula I accordingto the invention is for the dyeing of paper of all types, particularly bleached and sized, lignin-free paper, and also semi-cardboard and cardboard. These dyes are more especially suitable for dyeing unsized paper (for example serviettes) by virtue of the very high standard affinity of the dyes for this substrate.
The dyes according to the invention exhawst very well onto these substrates, the waste liquors - even with deep shades (up to above 1/1 RT - reference type strength) -being left colourless, a factor which is of great technical and ecological advantage, especially in view of the lZ~ Z'~
present-day effluent laws. The high degree of exhaustion is advantageous also with regard to good reproducibility of the shade. Furthermore, the degree of exhaustion is virtually unaffected by the hardness of the water. The dyeings are fast to wetting, that is to say, they exhibit no tendency to bleed when dyed paper in the wet state is brought into contact with moist white paper. This property is particularly desirable for serviettes, in the case of which it is foreseeable that the dyed paper in the wet condition (for example soaked with water, alcohol, tenside solution~ and so forth) will come into contact with other surfaces, such as textiles, paper, and the like~
which have to be protected against soiling.
The good affinity for paper ancd the high degree of exhaustion of the dyes according to the invention, combined with very good build-up properties, are of great advantage for the continuous dyeing of paper, and render possible a very broad and economical application of these novel dyes. They have the following advantages:
a) an easier and more rapid correction of the shade, and therefore less loss of paper not conforming to type (scrap~;
b) a better constancy of shade (no "tailing'l)j and c) there is no necessity to thoroughly clean the stirring vat after each batch, the working process simultaneously being shortened and the process thus optimized.
The yellow dyeings are brilliant and have very good fastness properties, especially fastness to light.
The dyes of the formula I are suitable also for dyeing leather materials by the widest variety of application methods, such as spraying, brushing and dipping, and for "
preparing inks of all types, such as for ball-point pens and for printing inks.
The invention is further illustrated by the following Examples without being limited by them. The temperatures are in degrees centigrade, 'parts' denote parts by weight, and percentages are per cent by weight.
The abbreviation RKN is a quali-ty designation, and indicates the degree of purity of the ceLlulose; the abbreviation SR = Schopper-Riegler denotes the freeness value.
Example 1: 16 parts of the condensation product from
5,6-benzoquinaldine and phthalic anhydride are introduced with 7 parts of N-methylolchloroacetamide at 0-5C into 100 parts of monohydrate, and the mixture is stirred until no starting material is visible in the thin-layer chromatogram. The reaction mixture is poured onto ice, whereupon the reaction product precipitates; it is then filtered off and washed neutral with water. The yield after drying is 20 parts of the compound ~ . ./ ~., ClCH CONHCH ~
2 2 ~ ~ OH
i i! ! .
/ ~N/ \ i \ / ~-o~
10 parts of this compound in 100 parts of pyridine are heated at 100C for 1 hour. The precipitated quinophthalone compound of the formula .;24442Z
. ~ CH2CONHCH2~ i~ OH
l L ~ /o\~ ICl~
is isolated by filtration and dried. It is very readilysoluble in water, and dyes paper in a brilliant, deeply-coloured, greenish-yellow shade having very good fastness 5 properties (particularly fastness to light), and exhibits an excellent build-up (colourless waste liquor).
Example 2: The procedure is carried out as in Example 1 except that the 100 parts of pyridine are replaced with 100 parts of a 20% aqueous trimethylamine solution. There is thus obtained the dye of the formula : _ _ 3) 3 2 1I NH CH2 H ~
, ~ \ /o~
i i1 . ~ - C19 This dye exhibits an excellent build-up on paper7 and the waste liquor is colourless.
When in Example 1 the 16 parts of the starting base are replaced with the equivalent amount of the respective starting bases (quinophthalones) listed in the following Table 1, column 2, the procedure otherwise being as described, there are obtained similar dyes, the shades of which on paper are given in eolumn 30 ;~Z,4~Z2 Table 1 1 2 3 `
Ex. Quinophthalones Shade on paper 3 ~ \ ~ yellow i1~si il 0 4 ~ sI ~ yellow .i1 i ~ IOH
CH3 . S ~./ N j 11 i yellow 0,~ \.~
2 2 ~ ~ OH
i i! ! .
/ ~N/ \ i \ / ~-o~
10 parts of this compound in 100 parts of pyridine are heated at 100C for 1 hour. The precipitated quinophthalone compound of the formula .;24442Z
. ~ CH2CONHCH2~ i~ OH
l L ~ /o\~ ICl~
is isolated by filtration and dried. It is very readilysoluble in water, and dyes paper in a brilliant, deeply-coloured, greenish-yellow shade having very good fastness 5 properties (particularly fastness to light), and exhibits an excellent build-up (colourless waste liquor).
Example 2: The procedure is carried out as in Example 1 except that the 100 parts of pyridine are replaced with 100 parts of a 20% aqueous trimethylamine solution. There is thus obtained the dye of the formula : _ _ 3) 3 2 1I NH CH2 H ~
, ~ \ /o~
i i1 . ~ - C19 This dye exhibits an excellent build-up on paper7 and the waste liquor is colourless.
When in Example 1 the 16 parts of the starting base are replaced with the equivalent amount of the respective starting bases (quinophthalones) listed in the following Table 1, column 2, the procedure otherwise being as described, there are obtained similar dyes, the shades of which on paper are given in eolumn 30 ;~Z,4~Z2 Table 1 1 2 3 `
Ex. Quinophthalones Shade on paper 3 ~ \ ~ yellow i1~si il 0 4 ~ sI ~ yellow .i1 i ~ IOH
CH3 . S ~./ N j 11 i yellow 0,~ \.~
6 ~ \ISIN~ 0~1 yellow
7 / ~ 1 yellow I_il i ~2~4~Z2 Table 1 (continuation) 1 ! 2 - - _ 3 Ex. Quinophthalones Shade on . _ paper ~ ~ \0/ ~ yellow 9 ~ i OH
. ~ / ~ \~ i yellow H ~ ~
Example 10: 17 parts of the amino-quinophthalone compound of the formula D~
il I
~/ \N~ \/
obtained by condensation of 5,6-benzoqulnaldine and 3-nitrophthalic anhydride, and subsequen~ reduction of the nitro group with sodium sulfide, are dissolved in ~.~4~4~z 200 parts of dimethylformamide, and to the solution at 50C
are added 6 parts of chloroacetyl chloride. When the thin-layer chromatogram shows no further starting material, 20 parts of pyridine are added. The mixture is stirred at 100C for 60 minutes and is then cooled. The dye of the formula ~ /c~ _ l \ ~ j OH
. N~ j ~HCcH2--~ ~ L C19 which has crystallised, is filtered with suction and dried.
It dyes paper in a deeply coloured yellow shade having very good fastness properties, and the waste liquor is left colourless.
When the procedure is carried out as in Example 10 except that the 17 parts of the starting base are replaced ~ith equivalent amounts of the respective amino-quinophthalone compounds listed in the following Table 2,column 2, there are obtained similar dyes, the shades of which on paper are shown in column 3.
- ~Z~L4Z~
Table 2 _ 2 3 Ex~ ~uinophthalones paper ~ OH yellow Il ., ,~
.~. OH yellow 12 ~/ H2 13 i \j/ ~- OH yellow 14 3 ~ i y e l l ow ~J~ ~
. _ _ .. _-- _ ~,Z~
.
Table 2 ~continuation) . 1 1 3 Shade on Ex. Quinophthalones paper ¦ 16 .~ \ ~ I ,z \~ H . ~ yellow . ~ 1H
7 .~ ~/NH2 .
_xample 18: 13 parts of the amino-quinophthalone compound according to Example 7 are suspended in 60 parts of nitrobenæene, and are reacted with 8.1 parts of 2,4,6-trichlorotriazine in the presence of 5.4 parts of N,N-dimethylaniline. The reaction product which has precipitated is filtered off with suction, washed, and then suspended in 80 parts of toluene. Reaction with 12.4 parts of 1-amino-3-dimethylaminopropane yields the intermediate of the formula !, ~!,.,.~j "H
~ CH2C1~2cH2 N (C~13) 2 O ~ ~ ~
N NH-cH2cH2cH2 ~ (C 3) 2 ~24~2~
which is quaternised with dimethyl sulfate in the customary manner. The resulting product of the formula \.~ )H . ~
~- N~ H-CH2cH2cH2-N (cll3) 3 L ~ c~l CH2CH -11 (CH3) 3 lCH3S0l(~) ¦ 2 dyes paper in deeply coloured yellow shades, and the waste liquor is left colourless.
Similar dyes having equally good dyeing properties are obtained by replacing in the above Example the 13 parts of the amino-quinophthalone compound with corresponding parts of an amino-quinophthalone from the Table 2, column 2, under otherwise the same reaction conditions.
Example 19: 50 parts of chemically bleached beechwood sulfite are mixed with 50 parts of bleached sulfite RKN 15 (freeness value 20 SR) and 2 parts of the quino-phthalone compound according to Example 1 in water (pH 6, water hardness 10 dH, temperature 20C, ratio of goods to liquor 1:4). After 15 minutes' stirring, paper sheets are produced on a ~rank sheet-former. The paper has been dyed in a very intense, brilliant, yellow shade which is fast to light. The degree of exhaustion attained is 100~/o~ and the waste liquor is colourless.
. ~ / ~ \~ i yellow H ~ ~
Example 10: 17 parts of the amino-quinophthalone compound of the formula D~
il I
~/ \N~ \/
obtained by condensation of 5,6-benzoqulnaldine and 3-nitrophthalic anhydride, and subsequen~ reduction of the nitro group with sodium sulfide, are dissolved in ~.~4~4~z 200 parts of dimethylformamide, and to the solution at 50C
are added 6 parts of chloroacetyl chloride. When the thin-layer chromatogram shows no further starting material, 20 parts of pyridine are added. The mixture is stirred at 100C for 60 minutes and is then cooled. The dye of the formula ~ /c~ _ l \ ~ j OH
. N~ j ~HCcH2--~ ~ L C19 which has crystallised, is filtered with suction and dried.
It dyes paper in a deeply coloured yellow shade having very good fastness properties, and the waste liquor is left colourless.
When the procedure is carried out as in Example 10 except that the 17 parts of the starting base are replaced ~ith equivalent amounts of the respective amino-quinophthalone compounds listed in the following Table 2,column 2, there are obtained similar dyes, the shades of which on paper are shown in column 3.
- ~Z~L4Z~
Table 2 _ 2 3 Ex~ ~uinophthalones paper ~ OH yellow Il ., ,~
.~. OH yellow 12 ~/ H2 13 i \j/ ~- OH yellow 14 3 ~ i y e l l ow ~J~ ~
. _ _ .. _-- _ ~,Z~
.
Table 2 ~continuation) . 1 1 3 Shade on Ex. Quinophthalones paper ¦ 16 .~ \ ~ I ,z \~ H . ~ yellow . ~ 1H
7 .~ ~/NH2 .
_xample 18: 13 parts of the amino-quinophthalone compound according to Example 7 are suspended in 60 parts of nitrobenæene, and are reacted with 8.1 parts of 2,4,6-trichlorotriazine in the presence of 5.4 parts of N,N-dimethylaniline. The reaction product which has precipitated is filtered off with suction, washed, and then suspended in 80 parts of toluene. Reaction with 12.4 parts of 1-amino-3-dimethylaminopropane yields the intermediate of the formula !, ~!,.,.~j "H
~ CH2C1~2cH2 N (C~13) 2 O ~ ~ ~
N NH-cH2cH2cH2 ~ (C 3) 2 ~24~2~
which is quaternised with dimethyl sulfate in the customary manner. The resulting product of the formula \.~ )H . ~
~- N~ H-CH2cH2cH2-N (cll3) 3 L ~ c~l CH2CH -11 (CH3) 3 lCH3S0l(~) ¦ 2 dyes paper in deeply coloured yellow shades, and the waste liquor is left colourless.
Similar dyes having equally good dyeing properties are obtained by replacing in the above Example the 13 parts of the amino-quinophthalone compound with corresponding parts of an amino-quinophthalone from the Table 2, column 2, under otherwise the same reaction conditions.
Example 19: 50 parts of chemically bleached beechwood sulfite are mixed with 50 parts of bleached sulfite RKN 15 (freeness value 20 SR) and 2 parts of the quino-phthalone compound according to Example 1 in water (pH 6, water hardness 10 dH, temperature 20C, ratio of goods to liquor 1:4). After 15 minutes' stirring, paper sheets are produced on a ~rank sheet-former. The paper has been dyed in a very intense, brilliant, yellow shade which is fast to light. The degree of exhaustion attained is 100~/o~ and the waste liquor is colourless.
Claims (13)
1. A quinophthalone compound of the formula I
(I) wherein Y is either a group of the formula or or a -CH=CH-CH=CH- group which is annularly-linked in the 5/6 or 7/8 position, said groups being unsubstituted or substituted by OH, C1-C4-alkyl or halogen, Z is a polyvalent bridge member selected from the group consisting of , -CH2-, -CONH-alkylene(C1-C4)- , -SO2NH-alkylene(C1-C4)-, -CH2-NHCO-alkylene(C1-C4)- and wherein each of the alkyl and alkylene groups appearing in said members is unsubstituted or is further substituted by OH, halogen, NH2 or Q is a cationic radical of the formula in which Rl to R6 independently of one another are each C1-C4-alkyl which is unsubstituted or substituted by OH, NH2, -N(C1-C4-alkyl)2 or phenyl, or R1 and R2 or R3 and R4 together with the N atom form in each case the morpholine, pyrrolidine, piperidine, piperazine, imidazole or triazole ring; or R3 and R4 and R5 together form the pyridinium ring, which is unsubstituted or substituted by C1-C4-alkyl, or form a triethylenediamine ring of the formula wherein R7 is C1-C4-alkyl which is unsubstituted or substituted by -NH2, -NH-C1-C4-alkyl or -N(C1-C4-alkyl)2 , m is 1 or 2, n is 1 or 2, and An is an anion;
and wherein the nucleus A is unsubstituted or is substituted by halogen, straight or branched chain C1-C4-alkyl, NO2, NH2, NHCO-C1-C4-alkyl, COO-Cl-C4-alkyl, C1-C4-alkoxy, S-C1-C4-alkyl, SO2-C1-C4-alkyl, NHCO-phenyl, COO-phenyl, phenoxy, thiophenoxy or SO2-phenyl and the nucleus B is unsubstituted or is substituted by halogen, straight or branched chain C1-C4-alkyl, OH, C1-C4-alkoxy, phenoxy, NH-C1-C4-.
alkyl, NH-phenyl, S-C1-C4-alkyl, thiophenoxy, SO2-C1-C4-alkyl, SO2-phenyl, COO-C1-C4-alkyl, or COO-phenyl.
(I) wherein Y is either a group of the formula or or a -CH=CH-CH=CH- group which is annularly-linked in the 5/6 or 7/8 position, said groups being unsubstituted or substituted by OH, C1-C4-alkyl or halogen, Z is a polyvalent bridge member selected from the group consisting of , -CH2-, -CONH-alkylene(C1-C4)- , -SO2NH-alkylene(C1-C4)-, -CH2-NHCO-alkylene(C1-C4)- and wherein each of the alkyl and alkylene groups appearing in said members is unsubstituted or is further substituted by OH, halogen, NH2 or Q is a cationic radical of the formula in which Rl to R6 independently of one another are each C1-C4-alkyl which is unsubstituted or substituted by OH, NH2, -N(C1-C4-alkyl)2 or phenyl, or R1 and R2 or R3 and R4 together with the N atom form in each case the morpholine, pyrrolidine, piperidine, piperazine, imidazole or triazole ring; or R3 and R4 and R5 together form the pyridinium ring, which is unsubstituted or substituted by C1-C4-alkyl, or form a triethylenediamine ring of the formula wherein R7 is C1-C4-alkyl which is unsubstituted or substituted by -NH2, -NH-C1-C4-alkyl or -N(C1-C4-alkyl)2 , m is 1 or 2, n is 1 or 2, and An is an anion;
and wherein the nucleus A is unsubstituted or is substituted by halogen, straight or branched chain C1-C4-alkyl, NO2, NH2, NHCO-C1-C4-alkyl, COO-Cl-C4-alkyl, C1-C4-alkoxy, S-C1-C4-alkyl, SO2-C1-C4-alkyl, NHCO-phenyl, COO-phenyl, phenoxy, thiophenoxy or SO2-phenyl and the nucleus B is unsubstituted or is substituted by halogen, straight or branched chain C1-C4-alkyl, OH, C1-C4-alkoxy, phenoxy, NH-C1-C4-.
alkyl, NH-phenyl, S-C1-C4-alkyl, thiophenoxy, SO2-C1-C4-alkyl, SO2-phenyl, COO-C1-C4-alkyl, or COO-phenyl.
2. A quinophthalone compound of the formula I according to Claim 1, wherein Y is the substituent of the formula
3. A quinophthalone compound of the formula I according to Claim 1, wherein Y is a -CH=CH-CH=CH- group which is annularly-linked in the 5/6- or 7/8-position.
4. A quinophthalone compound of the formula I according to Claim 1, wherein the nuclei A and B are unsubstituted or substituted by the grouping -(Z)m-(Q)n?An?n, or wherein the nucleus A is substituted by halogen.
5. A quinophthalone compound according to Claim 1, wherein Z is any one of the following bridge members: -NH-CH2CH(OH)-CH2-, -CH2-NHCO-alkylene(C1-C4)- especially -CH2NHCO-CH2- and particularly -NHCO-CH2- and .
6. A quinophthalone compound of the formula I according to Claim l, wherein Q is a cationic radical of the formula wherein R3, R4 and R5 independently of one another are each an unsubsti-tuted or substituted C1-C4-alkyl group, or R3, R4 and R5 together with the N atom form a heterocyclic ring.
7. A quinophthalone compound according to Claim 6, wherein Q is the pyridinium ring of the formula
8. A quinophthalone compound of the formula I according to Claim 1, wherein m is the number 1.
9. A quinophthalone compound of the formula I according to Claim 1, wherein Y is a substituent of the formula or a -CH=CH-CH=CH- group annularly-linked in the 5/6- or 7/8-position, the nucleus B is unsubstituted, the nucleus A is unsubstituted, or is substituted by halogen, or option-ally by the grouping -(Z)m-(Q)n?An?n , Z is a polyvalent bridge member of the formula -CH2NHCOCH2-, -NHCOCH2-or Q is a catonic radical of the formula and m is the number 1.
10. A process for dyeing and printing textile materials, paper and leather, and for the preparation of inks, which comprises the use of a quinophthalone compound of the formula I according to Claim 1.
11. A process according to Claim 10 for dyeing and printing paper of all types.
12. A process according to Claim 11 for dyeing and printing bleached, unsized, lignin-free paper (tissues).
13. A process according to Claim 12 for dyeing and printing polyacrylo-nitrile or cellulose materials.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH147482 | 1982-03-10 | ||
| CH1474/82-3 | 1982-03-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1244422A true CA1244422A (en) | 1988-11-08 |
Family
ID=4211328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000423081A Expired CA1244422A (en) | 1982-03-10 | 1983-03-08 | Quinophthalone compounds, processes for producing them, and their use as dyes |
Country Status (8)
| Country | Link |
|---|---|
| US (2) | US4588811A (en) |
| EP (1) | EP0088418B1 (en) |
| JP (1) | JPS58185651A (en) |
| AT (1) | ATE20247T1 (en) |
| AU (1) | AU1218083A (en) |
| CA (1) | CA1244422A (en) |
| DE (1) | DE3363875D1 (en) |
| ZA (1) | ZA831620B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5468862A (en) * | 1994-04-25 | 1995-11-21 | Warner-Jenkinson Company | Synthesis of Solvent Yellow 33 (D & C Yellow 11) with excess phthalic anhydride acid as a solvent |
| ATE467662T1 (en) * | 2005-03-18 | 2010-05-15 | Toyo Ink Mfg Co | PIGMENT DISPERGATOR, PIGMENT COMPOSITION AND PIGMENT DISPERSION |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2818409A (en) * | 1956-07-25 | 1957-12-31 | Du Pont | Quinophthalone dyes for hydrophobic fibers |
| US3023212A (en) * | 1960-06-30 | 1962-02-27 | Du Pont | Basic dyes of the quinophthalone series |
| DE1286666B (en) * | 1962-04-05 | 1969-01-09 | Hoechst Ag | Process for the production of water-soluble, cationic dyes |
| CH447422A (en) * | 1963-05-31 | 1967-11-30 | Sandoz Ag | Process for the production of dyes |
| US3274198A (en) * | 1963-06-14 | 1966-09-20 | Gen Aniline & Film Corp | Quaternary anthraquinone dyestuffs |
| US3492319A (en) * | 1966-06-21 | 1970-01-27 | Gaf Corp | Quaternary anthraquinone dyestuffs |
| CH523946A (en) * | 1969-11-19 | 1972-06-15 | Sandoz Ag | Process for the preparation of sulfonic acid group-free basic quinophthalone compounds |
| DE1963356A1 (en) * | 1969-12-18 | 1971-06-24 | Bayer Ag | Quinophthalone dyes |
| DE3111200A1 (en) * | 1981-03-21 | 1982-09-30 | Basf Ag, 6700 Ludwigshafen | CATIONIC DYES AND THEIR USE |
| DE3117956A1 (en) * | 1981-05-07 | 1982-11-25 | Basf Ag, 6700 Ludwigshafen | CATIONIC DYES AND THEIR USE FOR COLORING AND PRINTING PAPER |
| US4396769A (en) * | 1982-02-11 | 1983-08-02 | Ciba-Geigy Corporation | Process for preparing crystalline, non-dusting bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate |
| JPH06267986A (en) * | 1993-03-17 | 1994-09-22 | Hitachi Ltd | Method of manufacturing thin film transistor |
-
1983
- 1983-03-07 DE DE8383102210T patent/DE3363875D1/en not_active Expired
- 1983-03-07 AT AT83102210T patent/ATE20247T1/en not_active IP Right Cessation
- 1983-03-07 EP EP83102210A patent/EP0088418B1/en not_active Expired
- 1983-03-08 CA CA000423081A patent/CA1244422A/en not_active Expired
- 1983-03-09 AU AU12180/83A patent/AU1218083A/en not_active Abandoned
- 1983-03-09 ZA ZA831620A patent/ZA831620B/en unknown
- 1983-03-10 JP JP58040001A patent/JPS58185651A/en active Granted
-
1984
- 1984-11-19 US US06/672,869 patent/US4588811A/en not_active Expired - Fee Related
-
1985
- 1985-10-18 US US06/788,811 patent/US4656268A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE3363875D1 (en) | 1986-07-10 |
| ATE20247T1 (en) | 1986-06-15 |
| US4656268A (en) | 1987-04-07 |
| EP0088418B1 (en) | 1986-06-04 |
| AU1218083A (en) | 1983-09-15 |
| JPH0412305B2 (en) | 1992-03-04 |
| JPS58185651A (en) | 1983-10-29 |
| ZA831620B (en) | 1983-11-30 |
| EP0088418A3 (en) | 1983-11-16 |
| EP0088418A2 (en) | 1983-09-14 |
| US4588811A (en) | 1986-05-13 |
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